Stabilized hydrocarbon composition and stabilizing agent therefor



Patented Aug. 12, 1941 STABILIZED HYDROCARBON CODHOSITION ANDSTABILIZING AGENT THEREFOR Carl F. Prutton, Cleveland Heights, Albert K.Smith, Shaker Heights, and Delton R. Frey, East Cleveland, Ohio,assignors to The Lubri- Zol Corporation, Wic

of Ohio klifle, Ohio, a corporation No Drawing. Application March 6,1939,

Serial N0. 260,220

24 Claims. (01. 252-53) This invention relates, as indicated, to thestabilization of hydrocarbon compositions. The term hydrocarboncompositions as used-herein, is intended to include liquid compositionswhich are essentially derivatives of petroleum, naturally occurring oilsof the type represented by animal, vegetable and marine oils andderivatives of the same.

More specifically, this invention relates to the stabilization ofhydrocarbon compositions, such as lubricants which are usuallyessentially mineral oil. This invention also is applicable to thestabilization of lighter fractions of petroleum such as are used asfuels. 7

Certain subject matter disclosed but not claimed herein is disclosed andclaimed in copending applications Serial No. 260,221, filed March 6,1939, and Serial No. 395,234, filed-May 26, 1941.

It is well known that liquid hydrocarbon compositions of the characterabove identified are subject to deterioration as by oxidation andpolymerization, for example but not by way of limitation, during storageand handling and are also subject to deterioration which proceeds at amore rapid rate during use of these compositions.

For example, the various oils mentioned above 7 and the lighterfractionsused as fuels have a tendency on storage to oxidize,polymerize, or otherwise deteriorate to form gums and thelikej and whensuch compositions are used, particularly under conditions of hightemperature, de-

terioration proceeds at a more rapid rate to the production of gums,sludges and other oxidation and/or polymerization-products. Thisdeterioration is manifested by discoloration of the liquid hydrocarbonbody; the generation within the body of flocculent material; theprecipitation from the body of the more serious types of deteriorationproducts; such as sludge, and the deposit of var tend to causedeterioration of such oil composition. Oxidation and/ or sludgingofliquid hydrocarbon compositions employed as lubricants in suchengines'isusually accelerated by the rela-.

tively high temperatures to which such compositions are subjected. Thisis particularly true in engines of the Diesel type in which the opjectto thevarious conditions above named which crating temperatures aregenerally somewhat higher than those in the so-called ignition type.

It is a principal object of our invention, therefore, to provide for thestabilization of compositions of the character defined in order toreduce the tendency of the same to decompose particu .larly in themanner indicated.

It will also be observed that the addition agents employed for theprescribed purpose are in themselves new compositions of matter.

such compositions under conditions of use, by the inclusion therein of aminor proportion of the product resulting from the reaction of a hydroxyester or an organic hydroxy-acid with a reagent which comprisesphosphorus in tri-valent form and a halogen. It also comprises thesimilar use of certain derivatives of these reaction products.

As hereinafter more fully explained, the stabilization of certain typesof liquid hydrocarbon compositions and especially when the same are usedfor certain specific purposes, may be effected by the inclusion thereinof certain derivatives of the aforesaid reaction product or products orportions thereof, which derivatives may be prepared, for example, byhalogenation and/or treatment with an alkali or other base to form asalt, or ester-salt.

As previously stated, our invention contem plates the use, asstabilizing agents, of the products resulting from a. specifiedreaction. We therefore list below specific examples of the two classesof reactants which may be employed in the preparation of the productwhich we employ as the stabilizing addition agent.

The phosphorus and halogen containing reactants As indicated above, anymaterial which contains phosphorus in tri-valent form and a halogen,which material will react with a hydroxy ester, may be employed in thepreparation of an addition agent. Of these phosphorus andhalogencontaining reactants, PC13 will be found .to

be particularly useful and productive of suitable I addition agents.Other reactants of this class are as follows:

Phosphorus tri-bromide, PBra. Phosphorus tri-iodide, PIa

Phosphorous oxy-chloride, POCl Phosphorous sulpho-chloride,PSCl

the

Halogen derivatives of phosphin'e and organic substituted phosphines. e.g.

Phosphenyl chloride, (CsHs) PCi: Compounds of the classes:

(a) RPCI: and RR'PCl, and (b) ROPCI: and (R) (R'0)PC1 in which R and Rare organic radicles such as:

Aromatic. e. g.

Phenyl' v Cyclohexyl phenyl Alkylated phenyi Aliphatic, e. g. LaurylCetyl. y Cycloaliphatic, e., g. Cyclopentyl Cyclohexyl The hydrozwesters The esters which are suitable for use as one of the components ofthe reaction with'phosphorus and halogen containing reactants in thepreparation of the stabilizing addition agent of our invention may, forexample, be any of the esters produced by reacting any of the alcohols,

' and preferably any of the monoor di-hydroxy low molecular ,weightalcohols, such as any of the following:

- Methyl alcohol Ethyl alcohol Propyl alcohol Butyl alcohol Ethyleneglycol Propylene glycol Trimethylene glycol Cyclohexanol Benzyl'alcoholFurfuryl alcohol (1) Monobasic acids:

(a) Monohydroxy: e. g.' Glycollle acid Lactic acid Hydracrylic acidHydroxylbutyric acids 1 (b), Polyhydroxy: e. g.

Glyceric acid- Dihydroxypalmitic acid (2) Polybasic acid (a)Monohydroxy: e. g.

"Tartronic acid Malic acid Citramalic acid Citric acid b) Polyhydroxy:e. g.

Tartaric t V t Trihydroxy glutaric acid 7 In general, the esters of thelow molecular weight hydroxy-fatty acids are preferred.

We have found the methyl esters to be prefer able for our purpose inmost cases; I

The following-are illustrative of specific embodiments of our invention:a A material, which for purposes of convenience in referring to the sameherein we shall desighate as RM. L., is prepared bythe reaction ofmethyl lactate with PCla. The relative propor tions 'of. methyl lactateand PCI: used in :the preparation of P. M. L. are given in the-followingExample I (P, M. L.)

Methyl lactate 104 parts by weight PCla 45 parts by weight Weight ofproduct 74.5

Weight of material removed by distillation 31.8. Yield; 65% Average mol.wt 312 Boiling point 230 C. 10 Melting point Liquid at r 0 cm g Itemperature Sp. gr. at C -.1.252 Ref. index at 26 CL. 1.4365 Color Lightyellow 15 Phosphorus 10.9% Chlorine 1.12% Acid No 415 Soluble to extentof about 1% in Penna 150 (S. U. S. at 100 F.) neutral. Completelymiscible with .water and ethyl alcohol.

The methyl lactate is placed .in a reaction vessel equipped with anagitator and reflux condenser. The vessel and agitator are preferably ofglass or enamel. The PO13 is added slowly and l the temperature beginsto decrease, indicating that the PCI: has reacted to some extent withthe methyl lactate. The slow addition of PC13 accompanied by stirringuntil a decrease in temperature is noted insures against loss of PC]:whose boiling point is 76 C. andalso gives a higher yield than whenthese precautions are not taken. After the temperature of the react antshas begun to drop, heat is applied and the temperature of the reactantsis raised to 120 C. This temperature is maintained for 3-hours. A slightreaction is apparent until the mixture has :been heated at 120 C. forabout 2 hours and minutes. The mixture is stirred continuously all 'forliquid hydrocarbon compositions'or the end product may be distilled atatmospheric pressure and all of the material which distills over at 130table, aswell as the properties of the end product. 7

C. or less may be discarded. Whether the end product as producedfor therefined end product derived by removal of the more volatile products isused, depends largely upon the use for which the ultimate compositioncontaining the stabi lizing addition agent is designed. In general, theless volatile part of the reaction product, or

that part which contains combined phosphorus,

is preferred for our purpose.

We believe the reaction produces two general types of compounds: u

. (a) Chlorine-containing compounds, for example the type in whichchlorine has been substituted for the hydroxyl group of the hydroxy-.ester; and

(b) Phosphorus-containing compounds, for

example the type in which the ,hydroxyl group has lost hydrogen (whichforms HCl with chic rine removed from the P011100 that the omen (therei'ined material) to several diflerent repot the hydroxyl group becomesattached to a resentatlve commercial oils, and oils treated withphosphorus atom. other addition agents.

Composition Oxidationtcat Conradson I Cormm z ia Hen- "mm Viscosity8.18.3210 Naphtha Insoluble g: 5. g? 3? Methyl 110m Percent(leadstearste stearste P.M.L. Percent bronze) phenyl benzene a a 48 WHours ML 6 I oxide Original hm Orlzlnsl hour. 7 up for i0r100 hum a mg.111:.

treated 4 2 .00 .00 .00 541 00.4 10.4 14.0 0 00 -.20

' um-con'rmm'r 0.4. 11.00 010 '10s on.

treated I 1 4-- .00 .40 1.11 00.0 00.0 1.1 01.0 0 42 -.02 0 .00 .40 1.0101.1 11.0 50 .200 0 00 0 .00 .00 .00 1.02 000 10.1 100 11.0 45 111 -.011 .00 .00 .00 .01 1.20 001 000 0.2 01.0 0 04 --12 0 .00 00 .20 .41 200010 122 11.2 15.0 40 110 02 0 .50 00 20 .25 00 .10 1.10 02.1 00.0 11.100.0 .5 40 00 00051510100101. 0. .4 10. 10 0101011 OIL nsvmc A v. 1. or01 treated 11 .00 .04 100 42.1 .405 00 105 41.0 100 01 12..-... .00 .00.00 0.12 420 400 14.0 0.0 20.0 414 10. .00 .00 .00 .01 1.54 420 450 1 010.0 40.0 100 00 PENNSYLVANIA 0. A. 10. 40 MOTOR OIL e treated 15-.- .001.40 251 00.0 051 15s 4 0 2- 40 10.-- .00 1.01 201 00.0 000 104 4 0 2 as11 .00 .00 151 0.04 02.0 1040 20.5 4 5 0 -.00 10 .00 .00 .00 1.24 20201.4 04.0 150 4 4 0.1 -.o0 10-.- .00 .50 .25 1.10 2.00 10.0 00 0 042 4 0e 05 20....- .00 .50 20 .20 .00 1.40 2.00 01.0 04.0 10.0 4 0 0.0 10

rsrmsrnvmrs s A 11 10 MOTOR om .00 .10 .40 40.5 41.0 2.0 4(040 0 2 -.04.00 .00 .50 400 41.0 20 4 0 a -.01 .00 .10. 1.40. 450 000 01 210 5 00-1.40- .00 p .00 .20 .15 400 401 0.0 00.5 0 11 -.00 .50 20 .25 .21 1.10405 000 1.0 20.0 0 00 -1.40 00 20 .25 .00 -01 .01 41.2 40.1 a 0 00.0 010 11 .15 .10 1.10 41.0 000 1.4 200 0 45 -1. 15 .15 .00 .10 .01 400 40.05.1 04.0 Y 0 00 -.01

1545mm. e-did not produce 10 11min 48 hours.

b-did not produoeiil) 111s. hours.

lbr example in the reaction oi lactate The determinations which appearin the forewith P311, part a would be principally the methyl soinstable. such as, tor-example. Qonradson'carester ot-chlor propionic acidand part b prinhon. viscosity determinations, and naphtha in-.

cipally esters of phosphdrous acid I such as soluble. ,were determinedon samples prepared P(OC1H4COOCH0)0 and .RQHwCflflCOOQBfly w by ancaidation test procedure which is, in every It appears thattheconstltlients o! the reaction respect, similat to that prescribed by theStand- 0100001 described 44 41-401 444 responsible or aid 01 1001 4oxidation test, excepting 01141 4 the stabilising elect when the productis wed piece 0! ironfiire is submerged in the oil during in accordancewith our invention. 110 0100101- the test. 5'1 I most purposes, part ais not deleterious. and tor 45 The data given in the column headed"Corrosome purposes may even be advanta seoilly insion has 044determined in accordance with,

eluded. Part sis in 441150010000000140410 than the standa'rdlflhellcorrosion test using lead art b and may therefore-be easily separatedbronzeasthemctal.

from the latter, by distillation at atmospheric or A series or testssubstantially duplicating those subatmospheric pressure. 1 liven10104051440104 table but 011151 07 1 8 the The specific pmperties ivenin the table capunretlned P. M. 11., i. e.. the product immediatelytioned "Example No. I" are those for the reilned resultins from .thereaction between methyl lacmaterial. tate and P010. ndvlthoutdistillinsefl anyot The tollowinz table gives the resultsobtained the end product as hereinbeiore specified. were by theadditionoiminoraasoudsotPJLI-JIrunwithsubstantialiythesameresuitsasthcae given in the foregoing table.It would appear, therefore, that it is not necessary for most uses torefine the P. M. L. before it is used as an addition agent.

i; Another product which we shall hereinafter, for convenience, refer toas P. B. T. was made by reacting dibutyl tartrate with PCI; undersubstantially the conditions previously specified for the manufacture ofP. M. L., and the following is a table giving the proportions by weightof the reactants used and the properties of the end product.

Example II (P. B. T.)

Dibutyl 65 parts by weight PCla 11.6 parts by weight Weight of product".60 Weight of refinedmaterial.55.5 Yield 90% Boiling point 235 C.245 C.

Melting point Liquid atroomtemperature Tests on oils similar to thosegiven above in connection with the study of the properties of P. M. L.were run using P. B. T., and the latter was found to be substantially asefiective as P. M. L. v

Another material which we shall hereinafter, for convenience, refer toas P. M. C., was made by the reaction of trimethyl citrate with PCla.The proportions of reactants used and' the properties of the endproduct-are given inthe following table: I

' Example III (P. M. c'.)

Trimethyl citrate 500 parts by weight PCl: 75 parts by weight Weight ofproduct 480 I Weight of refined materiaL- 465 Yield 92% Melting point'80-100 C.-

Tests on this material in oil to determine its eflect similar to thosetests previously given in connection with the study of the eifect of P.M. L. were run and show that P. M. C. was similar to P. M. L., i e,eflective to retard deterioration of the oils. P. M. C. has a tendencyto be corrosive with respect at least to certain of the more sensitivemetals, and, therefore, when such metals are encountered it would beadvisable to employ minor amounts of corrosion inhibitors, such as thealkyl anriaryl phosphites, along with the P. M. C. I

Our invention also contemplates the employmentas a stabilizing agent ofthe reaction proda ucts which may be prepared by eitta' of the followingmethods, viz:

(a) Reacting a reagent, which comprises phosphorus in tri-valent formand halogen, with a mixture of hydroxy esters. a mixture of organichydroxy acids or a. mixture of one or more hydroxy esters with one ormore organic 'hydroxy acids.

(b) Reacting a reagent, which comprises phosphorus in tri-valent formandhalog en, with one or two molecules of a hydroxy ester oranorganichydroxy acid per molecule. ofreagent and then completing the reactionwith another re ctant oi. the class. consisting of hydroxy este s andorganic hydroxy acids diflerent from that which was initially employed.

v is stabilized the addition agents commonly em-- A lines such as Thereaction products thus prepared are especially desirable for use forcertain purposes on account of their complexity.

Very small amounts of our addition agents above identified, areeffective, in most. cases less than one percent, and usually a fractionof 1%, e. g. from about 0.001 to about 0.2% will be found most useful.For use in mineral lubricating oil (e. g. a motor oil for automobile,aviation, or Diesel engines) amounts from about 0.01% to about 0.1% aresuitable, and usually the reaction product with an alkali (e. g. sodium,

potassium, ammonium, or substituted ammonium, hydroxides) in aqueoussolution. Ester-salts may be formed by the partial saponiflcation ofesters of polybasic acids, 'e. g. the phosphoruscontaining reactionproduct of P01: with dibutyltartrate may be partly saponlfled withcaustic soda to form the corresponding butyl-sodium ester-salt. Similarsalts and ester salts of metals other than the alkali metals may beformed directly by reacting the ester with the metallic base, or morereadily by double-decomposition of the alkali salt (or ester-salt) witha salt of the othermetal. I

As above indicated, our addition agents are suitable for the purpose ofstabilizing liquid hydrocarbons generally, among which may be mentionedrefined mineral oils of the character generally employedas lubricants,lighter fractions andcuts such as are employed as fuels in Diesel typeengines and even lighter fractions and cuts which are commonlyidentified as gasoline. Other oils such as hydrogenated oils andvoltolized I oils may be similarly stabilized by the inclusion thereinof the above-mentioned addition agents.

The liquid hydrocarbon compositions which may be stabilized by the useof the addition agents hereinbefore specified need not be purehydrocarbons but may contain other addition agents such as extremepressure addition agents on the order of halogen, phosphorus and/orsulfur compounds, as well as corrosion inhibitors,

such as phosphorus compounds, etc. and other additions commonly,employed, such as pourpoint depressors and the like.

When a lighter fraction, as above indicated,

ployed in" such lighter fractions may also be present; as forexample,-"the variou s dopes" commonly employed in Diesel fuels, andantiknock compounds commonly employed in gasotetra-ethyl lead, ironcarbonyl, etc.

In general, the addition agents of this invention will-not be foundincompatible with com 'monly employed antioxidants such as are used ingasolines' and the like.

There may, however, be certain of these other addition agents whichmight be found incompatible with the addition agents of the presentinvention and in such cases, of course, the in-- compatible additionagent, whatever it may be, should be omitted, since it will usually befound that a compatible addition agent for the desired purpose will beavailable among others of those available.

Among the other addition agents with which the compounds of the presentinvention may be employed to advantage, as above stated, are the extremepressure addition agents, such as the halogen, phosphorus and/orsulfur-containing compounds. n

In general we have found that the addition agents of the presentinvention do not detri mentally affect the extreme pressurecharacteristics of a mineral lubricating oil, for example,

as other advantages flowing from the combination of the constituentsnamed. For example, it

is within the contemplation of our invention to add to a lighthydrocarbon fraction such as gasoline or Diesel fuel, minor amounts of aheavier which characteristics are the result of the presence therein ofthe extreme pressure addition agents above named. Moreover, where theaddition agents of the present invention have been tested in lubricatingcompositions which also contain certain other addition agents, theextreme pressure characteristics of the resultant composition has beensomewhat improved and such improvement has been traceable to thepresence therein of the compounds of the present invention.

Throughout the foregoing specification and in the appended claims,reference is made to "oil-' soluble and by such term, as used herein, itis liquid hydrocarbon such as refined mineral lubricating oil to whichhas been added a minor amount of the addition agents which characterizethe present invention. Such combination, 1. e., a? major proportion ofgasoline to which has been added a minor amountof a mineral oil oflubriintended to indicate the ability of the addition agent to form notonly true solutions with the oil to which the same are added, but alsothe ability to form therewith any form of substantially permanentlyhomogeneous composition.

With certain of the more difflcultly soluble addition agents to whichthis application relates,

it may be advantageous to employ a mutual solvent as one means forincreasing the "oil-solubility of the addition agents and to alsoincur-- porate the addition agents in the 011 base by specialhomogenizing apparatus, such as for example, that described in' CornellPatent No.

oil-soluble" to any extent and which may not be incorporated in such away as to effect any improvement in the oil, will obviously be excludedby the term oil-soluble, as employed in the specification and in theclaims.

In general, the addition agents prepared in the manner specified will besufllciently nonvolatile so as to find usefulness for the purposesspecified.

from the liquid hydrocarbon and those which will not be decomposed bythe temperatures which- In cases, however, where high temperatures areencountered, it will be best to select those which will neithersubstantially evaporate 1 compounded heavier hydrocarbon added to thelighter hydrocarbon fuel for optimum results will be found 'to be in thevicinity of 30%, i. e., in the range of from about 0.15% to 0.60%.

It will be observed that the addition agents mentioned above may begenerally classified as follows:

(1) nhr-oa'ooom OR'COORI (2) (OHM V oa oooiy and o-n'coom (a P-o-Iucoo1zI o-rucoori where R, R- and R, are organic radicles; and R, R -and R.are organic radicles, hydrogen, a metal, or a metallic radicle.

R! 1 \P0R'CO0R' 0-R'CO0RI (2 re 1 I o-a ooon where R", R, R and ,R' areorganic radicles and R. and R. are organic radicles, hydrogen, a

cating viscosity for lntema'l combustion engine 'use, along with aminoramount of the addition agents which characterize the present invention,produces a fuel for internalcombustion' engines which is particularlydesirable for ,use on account of the nature of the deposits left by thefuel in the combustion chamber, as well as the general performance ofthe fuel.

For proper results, when the compounded relatively-heavier liquidhydrocarbon is essentially mineral oil having a' viscosity of fromabout'50 to about 250 seconds Saybolt Universal at R, such compositionshould be added to the usually lighter hydrocarbon fuel of the typeboiling within the gasoline range in quantities varying from .05% to1.50% by volume. The amount of metal, or a metallic radicle.

which form.

which-the phosphorus is trivalent.

where R, R R and R are organic radicles and R and R are organicradicles, hydrogen, a metal, or a metallic radicle. I

- Other modes of applying the principle of our invention may be employedinsteadof the one explained, change being made as regards the materialsemployed, provided the ingredients stated by any of the following claimsor the equivalent of such stat ployed. v

We, therefore, particularly point out and distinctly claim as ourinvention:

1. A lubricating composition comprising a major proportion of mineraloil, the properties of which afiecting its use as a lubricant areimproved by the inclusion therein of a minor-proportion of anoil-soluble product resulting from ed ingredients be emvalent state, atleast one bond of which is attached to the radicle ORCO0R where R is anorganic radicle and R is selected from the class consisting of anorganic radicle, hydrogen, a metal and a metallic radicle.

"I. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting its use as a lubricant in thecrankcase of an internal combustion engine are improved by'the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of an ester of a mono-basic hydroxy acidwith a phosphorus and halogen-containing compound of the type in whichthe phosphorus is present in tri-valent form.

8. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting its use as a lubricant in thecrankcas of an internal combustion engine are improved by the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of an ester of a saturated mono-basichydroxy acid with a phosphorus and halogen-containing compound of thetype in which the phosphorus is present in tri-valent form.

9. A lubricating composition comprising a major proportion of mineraloil, the properties the reaction hydroxy-ester With a 1 of whichaifecting its use as a lubricant in the major proportion of mineral oil,the properties of which afiecting its use as a lubricant in thecrank-case of an internal combustion engine are improved by .theinclusion therein of a minor proportion of the phosphorus-containingproduct resulting from the reaction of an ester of an organichydroxy-acid with a. phosphorus and halogen containing compound of thetype in the phosphorus is present in tri-valent 3. A lubricatingcomposition comprising a crankcase of an internal combustion engine areimproved by the inclusion therein of a minor proportion of thephosphorus-containing product resulting from the reaction of an ester ofa low molecular weight saturated mono-basic hydroxy acid with aphosphorus and halogen-containing compound of the type in which thephosphorus is present in tri-valentform.

10. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting itsuse as a lubricant in thecrankcaseof an internal combustion engine are improvedby the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of an ester of a major proportion of mineraloil, the properties of which aflecting its use as alubricant in thecrankq'case of an internal combustion engine are improved by theinclusion therein of a minor pro- Iportionof' the phosphorus-containingproduct low molecular weight saturated mono-basic hydroxy acid and amono or di-hydric alcohol with a phosphorus and halogen-containingcompound of the type in which the phosphorus is present improved by theinclusion therein of a minor crankecase ot aninternal combustion engineare improved by the inclusion therein of a minor proportion of thephosphorus-containing product relsulting from the reaction of PC13 withtrimethyl citrate. I

@5. A lubricating composition comprising a major proportion oflubricating oil, the resistance ,of which to the formation ofdeleterious products when exposed to high temperatures under condi-'tions of use is improved by the inclusioriitherein ot aminor'proportionof an oilesoluble, phosphorus-bearing derivative of anorganic hydroxy-acid which derivative is obtained irom the reactionproduct oi th acid with a phosphorus-- and halogen-containing reagent ofthe type in 6. A composition oi? matter comprising -a major proportionof a liquid hydrocarbon having included in solution therein aminor'proportion oi' a compound containing phosphorus in -triproportionof the phosphorus-containing product resulting from the reaction of anester of a low molecular weight saturated -mono-b asic hydroxy acidand alow molecular weight mono ordi-hydric alcohol with a phosphorus andhalogen-Icontaining. compound of the type in which the phosphorus ispresent in tri-valent form.

12. A lubricating composition comprising a improved by the inclusiontherein '0! a minor- I proportion of the phosphorus-containing productresulting from the reaction of an ester of, a low molecular weightsaturated mono-basic hydroxy acid and a low molecular weightmono-hydric,

13. A lubricating composition comprising/a improved by the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of an ester of apolybasic hydroxy acid witha phosphorus and halogen-containing compound of the type in which thephosphorus is present intri-valent form.

14'. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting its use as a lubricants-in thecrankcase of an internal combustion engine are improved by the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of an ester of a a saturated poly-basichydroxy acid with a phosphorus and halogen-containing compound of thetype in which the phosphorus is present in tri-valent form.

15. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting its use as a lubricant in thecrankcase of an internal combustion engine are improved by the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of anester of a low molecular weightsaturated poly-basic hydroxy acid with a phosphorus andhalogen-containing compound of the type in which the phosphorus ispresent in tri-valent form.

16. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting its use as a lubricant in thecrankcase of an internal combustion engine are improved by the inclusiontherein of a minor proportion of the prosphorus-containing prodhydricalcohol with a phosphorus and halogencontaining compound of the type inwhich the phosphorus is present in tri-valent form. a 19. A lubricatingcomposition comprising a major proportion of mineral oil, the propertiesof which afiecting its use as a lubricant are improved by ,the inclusiontherein of-from an effective amount to about 1% of an oil-solubleproduct resulting from the reaction of a hydroxy-ester with a phosphorusand halogen containing compound of the type in which the phosphorus ispresent in the tri-valent form.

20. A lubricating composition comprising a major proportion of mineraloil which has been stabilized by the inclusion therein of from about.001% to about 2% of an oil-soluble product resulting from the reactionof a hydroxy-ester with a phosphorus and halogencontaining compound ofthe type in which the phosphorus is present in the tri-valent form.

21. A lubricating composition comprising a major proportion of alubricating oil the resistance of which to oxidation is improved by theinclusion therein of from about .0l% to about .1% of the productresulting from the reaction of a hydroxy-ester with a phosphorus andhalogen containing compound of the type in which the phosphorus ispresent in tri-valent form. i

22. A composition of matter comprising a major proportion of a liquidhydrocarbon having included in solution therein from an effective amountto about 1% of a compound containing phosphorus in tri-valent state, atleast one uct resulting from the reaction of an ester of al lowmolecular weightsaturated poly-basic hydroxy acid and a monoor di-hydricalcohol with a phosphorus andhalogen-containing compound of the type inwhich the phosphorus is present in tr'i-valent form.

17. A lubricating composition comprisingv a major proportion of mineraloil, the properties of which affecting its use as a lubricant in thecrankcase of an internal combustion engine are improved by the inclusiontherein of a minor proportion of the phosphorus-containing productresulting from the reaction of an ester of a low molecular weightsaturated poly-basic hydroxy acid and a low moleculanweight monoordi-hydric alcohol with a phosphorus and halogen-containing compound ofthe type in which the phosphorus is present in tri-valent form.

18. A lubricating composition comprising a major proportion of mineraloil, the properties of which affecting its use as a lubricant in thecrankcase of an internal combustion engine are improved by the inclusiontherein of a. minor proportion of the phosphorus-containing prodbond ofwhich is attached to the radicle -ORCOOR', where R isan organic radicleand R. is selected from the class consistingof an organic radicle,hydrogen, a metal and a metallic radicle.

23. A composition of matter vcomprising a major proportion of a liquidhydrocarbon which has. been stabilized by the inclusion therein or fromabout .001% to about .2% of a compound containing phosphorus in-tri-valent state, at

least one bond of which is attached to the radicle --ORCOOR, where R isan organic radicle and R is selected from the class consisting of anorganic radicle, hydrogen, a metal and a metallic radicle.

uct resulting from the reaction of an-ester of a low molecular weightsaturated poly-basichydroxy acid'and a low molecular weight mono- 24. Acomposition of matter comprising a major proportion of a liquidhydrocarbon, the

resistance of which to oxidation has been improved by the inclusion insolution therein 01 from about .01% to about .1% of a compoundcontaining phosphorus in tri-valent state, at

